EP0097861A1 - Aromatic polyester carbonate with impact strenght, and process for its preparation - Google Patents

Aromatic polyester carbonate with impact strenght, and process for its preparation Download PDF

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EP0097861A1
EP0097861A1 EP83105763A EP83105763A EP0097861A1 EP 0097861 A1 EP0097861 A1 EP 0097861A1 EP 83105763 A EP83105763 A EP 83105763A EP 83105763 A EP83105763 A EP 83105763A EP 0097861 A1 EP0097861 A1 EP 0097861A1
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solvent
hydroxyphenyl
bis
aromatic polyester
aromatic
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EP0097861B1 (en
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Dieter Dr. Freitag
Ludwig Dr. Bottenbruch
Manfred Dr. Schmidt
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups

Definitions

  • Aromatic polyester carbonates are known (GS Kolesnikov et. Al., J. Polym. Sci. USSR, Vol. 9, 1705-1711 (1967); US 30 30 331, 31 69 121, 3409 704, DE-OS 27 14 544, 27 58 030, 30 07 934). They are preferably produced from diphenolate, dicarboxylic acid dichloride and phosgene using the two-phase interface process.
  • the invention relates to a process for the preparation of aromatic polyester carbonates with a molar ratio of ester to carbonate groups from 20: 1 to 1:20, preferably from 9: 1 to 2: 8, characterized in that a solvent-containing mixture which a) aromatic polyester and b) aromatic polycarbonate in the desired ratio and 5 to 80, preferably 20 to 70, wt .-% organic solvent (based on solvent-containing mixture), with the deduction of the solvent - optionally under reduced pressure - preferably starting in a temperature range of 150 to 280 ° C, in particular from 200 to 260 ° C - while maintaining the liquid state at a temperature of 300 to 420 ° C, preferably from 310 to 360 ° C, heated until the reaction product only has a glass transition temperature.
  • a solvent-containing mixture which a) aromatic polyester and b) aromatic polycarbonate in the desired ratio and 5 to 80, preferably 20 to 70, wt .-% organic solvent (based on solvent-containing mixture), with the deduction of the solvent - optional
  • the solvent content of the mixture can be reduced by an upstream evaporation.
  • the transesterification is advantageously carried out in a kneader or evaporation extruder. With intensive mixing, the temperature is increased and the pressure is reduced, preferably continuously. Can be advantageous carry out the process in several stages, in the first stage the mixture is freed from the solvent under normal pressure or reduced pressure to about 5% by weight and then in the last treatment zone - preferably in an extruder with degassing nozzle - at reduced pressure residual solvent removed. As a rule, after a residence time of 20 to 200 seconds, preferably 25 to 120 seconds, the transesterification is complete in the last treatment zone.
  • the glass transition temperature can be determined, for example, by shear modulus measurements on films made from solutions.
  • Extruders preferred for the process according to the invention are e.g. described in DE-OS 14 04 984 and in DE-AS 12 09 741 (examples) and 14 04 237.
  • Aromatic polyesters (a) for the purposes of the invention are polyesters containing iso- and / or terephthalic acid residues, diphenol residues, residues of chain terminators and optionally branching agents with relative viscosities from 1.18 to 2.0, preferably from 1.2 to 1.5 ( measured on a solution of 0.5 g polyester in 100 ml dichloromethane solution at 25 ° C). You will e.g. in the monograph "Polyester” by V.V. Korshak and S.V. Vinogradova, Pergamon Press, Oxford 1965, pp. 494, 485-486, 454-455.

Abstract

Aus Lösungen aromatischer Polyester und aromatischer Polycarbonate lassen sich durch Eindampfen aromatische Polyestercarbonate herstellen.Aromatic polyester carbonates can be produced by evaporation from solutions of aromatic polyesters and aromatic polycarbonates.

Description

Die Erfindung betrifft aromatische Polyestercarbonate mit erhöhter Kerbschlagzähigkeit und ein Verfahren zu ihrer Herstellung durch Eindampfen von Lösungen, die sowohl aromatischen Polyester als auch aromatisches Polycarbonat enthalten.The invention relates to aromatic polyester carbonates with increased impact strength and a process for their preparation by evaporating solutions which contain both aromatic polyester and aromatic polycarbonate.

Aromatische Polyestercarbonate sind bekannt (G.S. Kolesnikov et. al., J. Polym. Sci. USSR, Vol. 9, 1705-1711 (1967); US 30 30 331, 31 69 121, 3409 704, DE-OS 27 14 544, 27 58 030, 30 07 934). Sie werden vorzugsweise nach dem Zweiphasengrenzflächenverfahren aus Diphenolat, Dicarbonsäuredichlorid und Phosgen hergestellt.Aromatic polyester carbonates are known (GS Kolesnikov et. Al., J. Polym. Sci. USSR, Vol. 9, 1705-1711 (1967); US 30 30 331, 31 69 121, 3409 704, DE-OS 27 14 544, 27 58 030, 30 07 934). They are preferably produced from diphenolate, dicarboxylic acid dichloride and phosgene using the two-phase interface process.

Während z.B. die Coextrusion aromatischer Polyester und aromatischer Polycarbonate zu Polyester/Polycarbonat-Legierungen führt (vgl. z.B. DE-OS 22 11 202, US 33 98 212, 33 99 172), findet überraschenderweise in Gegenwart von Lösungsmitteln bei hohen Temperaturen eine Umesterung statt. Das erfindungsgemäße Verfahren stellt eine elegante Methode der Herstellung aromatischer Polyestercarbonate dar.While, for example, the coextrusion of aromatic polyesters and aromatic polycarbonates leads to polyester / polycarbonate alloys (cf. e.g. DE-OS 22 11 202, US 33 98 212, 33 99 172), surprisingly, a transesterification takes place in the presence of solvents at high temperatures. The process according to the invention represents an elegant method of producing aromatic polyester carbonates.

Gegenstand der Erfindung ist ein Verfahren zur Herstellung aromatischer Polyestercarbonate mit einem molaren Verhältnis von Ester- zu Carbonatgruppen von 20:1 bis 1:20, vorzugsweise von 9:1 bis 2:8, dadurch gekennzeichnet, daß man eine lösungsmittelhaltige Mischung, die a) aromatischen Polyester und b) aromatisches Polycarbonat im gewünschten Verhältnis und 5 bis 80, vorzugsweise 20 bis 70, Gew.-% organisches Lösungsmittel (bezogen auf lösungsmittelhaltige Mischung) enthält, unter Abzug des Lösungsmittels - gegebenenfalls unter vermindertem Druck - vorzugsweise beginnend in einem Temperaturbereich von 150 bis 280°C, insbesondere von 200 bis 260°C - unter Aufrechterhaltung des flüssigen Zustands auf eine Temperatur von 300 bis 420°C, vorzugsweise von 310 bis 360°C, erhitzt, bis das Reaktionsprodukt nur noch eine Glasübergangstemperatur aufweist.The invention relates to a process for the preparation of aromatic polyester carbonates with a molar ratio of ester to carbonate groups from 20: 1 to 1:20, preferably from 9: 1 to 2: 8, characterized in that a solvent-containing mixture which a) aromatic polyester and b) aromatic polycarbonate in the desired ratio and 5 to 80, preferably 20 to 70, wt .-% organic solvent (based on solvent-containing mixture), with the deduction of the solvent - optionally under reduced pressure - preferably starting in a temperature range of 150 to 280 ° C, in particular from 200 to 260 ° C - while maintaining the liquid state at a temperature of 300 to 420 ° C, preferably from 310 to 360 ° C, heated until the reaction product only has a glass transition temperature.

Der Lösungsmittelgehalt der Mischung kann durch eine vorgeschaltete Eindampfung vermindert werden. Die Umesterung wird zweckmäßigerweise in einem Kneter oder Ausdampfextruder durchgeführt. Unter intensivem Mischen werden - vorzugsweise kontinuierlich - die Temperatur erhöht und der Druck gesenkt. Vorteilhaft läßt sich das Verfahren in mehreren Stufen durchführen, wobei man in der ersten Stufe die Mischung unter Normaldruck oder vermindertem Druck bis auf ca. 5 Gew.-% vom Lösungsmittel befreit und anschließend in der letzten Behandlungszone - vorzugsweise in einem Extruder mit Entgasungsstutzen - bei vermindertem Druck das restliche Lösungsmittel entfernt. In der Regel ist nach einer Verweilzeit von 20 bis 200 sec., vorzugsweise von 25 bis 120 sec., in der letzten Behandlungszone die Umesterung vollständig. Die Opaleszenz, die durch die unterschiedlichen Brechungsindices der beiden Ausgangspolykondensate zustande kommt, verschwindet im Laufe der Reaktion. Nach erfolgter Umesterung zeigt das Auftreten einer einzigen Glasübergangstemperatur an, daß aus der eingesetzten Mischung ein Mischkondensat entstanden ist. Verglichen mit nach dem Zweiphasengrenzflächenverfahren hergestellten aromatischen Polyestercarbonaten, weisen die erfindungsgemäß hergestellten aromatischen polyestercarbonate deutlich erhöhte Kerbschlagzähigkeit und Fließfähigkeit auf.The solvent content of the mixture can be reduced by an upstream evaporation. The transesterification is advantageously carried out in a kneader or evaporation extruder. With intensive mixing, the temperature is increased and the pressure is reduced, preferably continuously. Can be advantageous carry out the process in several stages, in the first stage the mixture is freed from the solvent under normal pressure or reduced pressure to about 5% by weight and then in the last treatment zone - preferably in an extruder with degassing nozzle - at reduced pressure residual solvent removed. As a rule, after a residence time of 20 to 200 seconds, preferably 25 to 120 seconds, the transesterification is complete in the last treatment zone. The opalescence that results from the different refractive indices of the two starting polycondensates disappears in the course of the reaction. After the transesterification, the occurrence of a single glass transition temperature indicates that a mixed condensate has formed from the mixture used. Compared with aromatic polyester carbonates produced by the two-phase interface process, the aromatic polyester carbonates produced according to the invention have significantly higher notched impact strength and flowability.

Die Glasübergangstemperatur kann beispielsweise durch Schubmodulmessungen an aus Lösungen hergestellten Folien bestimmt werden.The glass transition temperature can be determined, for example, by shear modulus measurements on films made from solutions.

Für das erfindungsgemäße Verfahren bevorzugte Extruder werden z.B. in der DE-OS 14 04 984 und in den DE-AS 12 09 741 (Beispiele) und 14 04 237 beschrieben.Extruders preferred for the process according to the invention are e.g. described in DE-OS 14 04 984 and in DE-AS 12 09 741 (examples) and 14 04 237.

Für das erfindungsgemäße Verfahren bevorzugte organische Lösungsmittel sind beispielsweise Methylenchlorid, Chloroform, Tetrachlorethane, Trichlorethylen, Tetrachlorethylen, Chlorbenzol, Dichlorbenzol, Toluol, Xylol, Anisol, oder deren Mischungen (vgl. DE-OS 15 70 533, 15 95 762, 21 16 974, 21 13 345, 25 00 092, GB 10 79 821 und US 35 11 514).Preferred organic solvents for the process according to the invention are, for example, methylene chloride, Chloroform, tetrachloroethane, trichlorethylene, tetrachlorethylene, chlorobenzene, dichlorobenzene, toluene, xylene, anisole, or their mixtures (cf. DE-OS 15 70 533, 15 95 762, 21 16 974, 21 13 345, 25 00 092, GB 10 79 821 and US 35 11 514).

Aromatische Polyester (a) im Sinne der Erfindung sind Polyester enthaltend Iso- und/oder Terephthalsäurereste, Diphenolreste, Reste von Kettenabbrechern und gegebenenfalls von Verzweigungsmitteln mit relativen Viskositäten von 1,18 bis 2,0, vorzugsweise von 1,2 bis 1,5 (gemessen an einer Lösung von 0,5 g Polyester in 100 ml Dichlormethan-Lösung bei 25°C). Sie werden z.B. in der Monographie "Polyester" von V.V. Korshak und S.V. Vinogradova, Pergamon Press, Oxford 1965, S. 494, 485-486, 454-455 beschrieben.Aromatic polyesters (a) for the purposes of the invention are polyesters containing iso- and / or terephthalic acid residues, diphenol residues, residues of chain terminators and optionally branching agents with relative viscosities from 1.18 to 2.0, preferably from 1.2 to 1.5 ( measured on a solution of 0.5 g polyester in 100 ml dichloromethane solution at 25 ° C). You will e.g. in the monograph "Polyester" by V.V. Korshak and S.V. Vinogradova, Pergamon Press, Oxford 1965, pp. 494, 485-486, 454-455.

Bevorzugte Diphenole für die Herstellung der aromatischen Polyester (a) sind Verbindungen der Formel

Figure imgb0001
worin Z einen zweiwertigen ein- oder mehrkernigen aromatischen Rest mit 6-30 C-Atomen bedeutet, wobei Z derart gebaut ist, daß die beiden OH-Gruppen direkt an je ein C-Atom des aromatischen Systems gebunden sind.Preferred diphenols for the preparation of the aromatic polyesters (a) are compounds of the formula
Figure imgb0001
 where Z is a divalent mono- or polynuclear aromatic radical having 6-30 C atoms, Z being constructed in such a way that the two OH groups are bonded directly to one C atom of the aromatic system.

Besonders bevorzugte Diphenole sind Verbindungen der Formel

Figure imgb0002
in der

  • Y eine Einfachbindung, einen Alkylen- oder Alkylidenrest mit 1-7 C-Atomen, einen Cycloalkylen- oder Cycloalkylidenrest mit 5-12 C-Atomen, -0-, -S-, -S-, -SO2-, oder -C- bedeutet, O 0
  • sowie deren kernalkylierte und kernhalogenierte Derivate z.B.
    • Hydrochinon,
    • Resorcin,
    • Dihydroxydiphenyle,
    • Bis-(hydroxyphenyl)-alkane,
    • Bis-(hydroxyphenyl)-cycloalkane,
    • Bis-(hydroxyphenyl)-sulfide,
    • Bis-(hydroxyphenyl)-ether,
    • Bis-(hydroxyphenyl)-ketone,
    • Bis-(hydroxyphenyl)-sulfoxide,
    • Bis-(hydroxyphenyl)-sulfone und
    • '-Bis-(hydroxyphenyl)-diisopropylbenzole
    sowie deren kernalkylierte und kernhalogenierte Verbindungen. Diese und weitere geeignete Diphenole sind z.B. in den US-Patentschriften 3 028 365, 3 275 601, 3 148 172, 3 062 781, 2 991 273, 3 271 367, 2 999 835, 2 970 131 und 2 999 846, in den deutschen Offenlegungsschriften 1 570 703, 2 063 050, 2 063 052, 2 211 956, 2 211 957, der franz. Patentschrift, 1 651 518 und in der Monographie H. Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York 1964, beschrieben.
Particularly preferred diphenols are compounds of the formula
Figure imgb0002
 in the
  • Y is a single bond, an alkylene or alkylidene radical with 1-7 C atoms, a cycloalkylene or cycloalkylidene radical with 5-12 C atoms, -0-, -S-, -S-, -SO 2 -, or -C - means O 0
  • and their nuclear alkylated and nuclear halogenated derivatives, for example
    • Hydroquinone,
    • Resorcinol,
    • Dihydroxydiphenyls,
    • Bis (hydroxyphenyl) alkanes,
    • Bis (hydroxyphenyl) cycloalkanes,
    • Bis (hydroxyphenyl) sulfides,
    • Bis (hydroxyphenyl) ether,
    • Bis (hydroxyphenyl) ketones,
    • Bis (hydroxyphenyl) sulfoxides,
    • Bis (hydroxyphenyl) sulfones and
    • '-Bis (hydroxyphenyl) diisopropylbenzenes
    and their nuclear alkylated and nuclear halogenated compounds. These and other suitable diphenols are described, for example, in US Pat. Nos. 3,028,365, 3,275,601, 3,148,172, 3,062,781, 2,991,273, 3,271,367, 2,999,835, 2,970,131 and 2,999,846 German Offenlegungsschriften 1 570 703, 2 063 050, 2 063 052, 2 211 956, 2 211 957, the French. Patent, 1,651,518 and in of the monograph H. Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York 1964.

Die wichtigsten Diphenole seien nachfolgend namentlich aufgezählt:

  • Bisphenol A, Tetramethylbisphenol A, 1,1-Bis-(4-hydroxyphenyl)-isobutan, 1,1-Bis-(4-hydroxyphenyl)-cyclohexan, 4,4'-Dihydroxydiphenylsulfid, 4,4'-Dihydroxydiphenyl, 4,4'-Dihydroxydiphenylsulfon sowie deren di- und tetrahalogenierte Derivate. Besonders bevorzugt ist Bisphenol A. Es können auch beliebige Mischungen der vorgenannten Diphenole verwendet werden.
The most important diphenols are listed below:
  • Bisphenol A, tetramethyl bisphenol A, 1,1-bis (4-hydroxyphenyl) -isobutan, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-D ihydroxydiphenylsulfid, 4,4'-dihydroxydiphenyl, 4 , 4'-Dihydroxydiphenylsulfone and their di- and tetrahalogenated derivatives. Bisphenol A is particularly preferred. Any mixtures of the aforementioned diphenols can also be used.

Bevorzugte aromatische Polyester (a) enthalten Iso- und Terephthalsäurereste im Verhältnis 7:3 bis 3:7, vorzugsweise etwa 1:1.Preferred aromatic polyesters (a) contain iso- and terephthalic acid residues in a ratio of 7: 3 to 3: 7, preferably about 1: 1.

Aromatische Polycarbonate (b) im Sinne der Erfindung sind Homo- und Copolycarbonate auf Basis der Diphenole I bzw. II, Phosgen, Kettenabbrechern und gegebenenfalls Verzweigungsmitteln und mit einem als Gewichtsmittel bestimmten Molekulargewicht M von 10 000 bis 200 000, vorzugsweise von 20 000 bis 80 000, ermittelt durch Lichtstreuung.Aromatic polycarbonates (b) in the context of the invention are homo- and copolycarbonates based on diphenols I and II, phosgene, chain terminators and optionally branching agents and with a molecular weight M determined as weight average of from 10,000 to 200,000, preferably from 20,000 to 80 000, determined by light scattering.

Außer den oben für die Herstellung der Polyester (a) genannten Diphenole sind für die Herstellung der Polycarbonate (b) die folgenden Diphenole besonders bevorzugt:

  • 2,4-Bis-(4-hydroxyphenyl)-2-methylbutan, 2,2-Bis-(3-methyl-4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propan und α,α-'Bis-(4-hydroxyphenyl)-p-diisopropylbenzol. Bevorzugte Polycarbonate (b) sind Copolycarbonate auf Basis von Bisphenol A und einem der oben als bevorzugt genannten Diphenole; besonders bevorzugt sind Polycarbonate, die als Diphenolreste nur Bisphenol-A-reste enthalten.
In addition to the diphenols mentioned above for the preparation of the polyesters (a), the following diphenols are particularly preferred for the preparation of the polycarbonates (b):
  • 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) ) -propane and α, α-'bis (4-hydroxyphenyl) -p-diisopropylbenzene. Preferred polycarbonates (b) are copolycarbonates based on bisphenol A and one of the diphenols mentioned above as preferred; polycarbonates which contain only bisphenol A residues as diphenol residues are particularly preferred.

Die erfindungsgemäß hergestellten Polyestercarbonate finden vornehmlich zur Herstellung von Formkörpern Verwendung, die hohe Wärmeformbeständigkeit und hohe Kerbschlagzähigkeit aufweisen sollen, z.B. Steckerleisten, Lampenhalterungen, Scheinwerfergehäuse.The polyester carbonates produced according to the invention are primarily used for the production of moldings which are said to have high heat resistance and high impact strength, e.g. Power strips, lamp holders, headlight housings.

Die Verarbeitung erfolgt in der Regel durch Spritzguß bei Massetemperaturen von 280 bis 360°C und bei Formtemperaturen von 100 bis 200°C.Processing is usually carried out by injection molding at melt temperatures of 280 to 360 ° C and at mold temperatures of 100 to 200 ° C.

BeispieleExamples

Der in den nachfolgenden Beispielen in Form seiner 10 gew.- %igen Lösung in Methylenchlorid/Chlorbenzol (Gewichtsverhältnis 1:1) eingesetzte aromatische Polyester "APE" ist ein Polyester aus Bisphenol-A, Iso- und Terephthalsäure (Molverhältnis Iso-/Terephthalsäure = 1/1) sowie p-tert. Butylphenol als Kettenabbrecher mit einer relativen Lösungsviskosität ηrel = 1.301, gemessen in 0,5 gew.-%iger Lösung in Methylenchlorid bei 25°C.The aromatic polyester "APE" used in the following examples in the form of its 10% by weight solution in methylene chloride / chlorobenzene (weight ratio 1: 1) is a polyester made from bisphenol-A, iso- and terephthalic acid (molar ratio iso- / terephthalic acid = 1/1) and p-tert. Butylphenol as chain terminator with a relative solution viscosity η rel = 1.301, measured in 0.5% by weight solution in methylene chloride at 25 ° C.

Das in den nachfolgenden Beispielen in Form seiner 10 gew.- %igen Lösung in Methylenchlorid/Chlorbenzol (Gewichtsverhältnis 1:1) eingesetzte Polycarbonat "PC" ist ein Polycarbonat aus Bisphenol-A, Phosgen und p-tert. Butylphenol als Kettenabbrecher mit einer relativen Lösungsviskosität ηrel = 1.300, gemessen in 0,5 gew.-%iger Lösung in Methylenchlorid bei 25°C.The polycarbonate "PC" used in the following examples in the form of its 10% strength by weight solution in methylene chloride / chlorobenzene (weight ratio 1: 1) is a polycarbonate composed of bisphenol-A, phosgene and p-tert. Butylphenol as a chain terminator with a relative solution viscosity η rel = 1,300, measured in 0.5% by weight solution in methylene chloride at 25 ° C.

Die Prüfung der Kerbschlagzähigkeit ak nach Charpy erfolgte an Normkleinstäben gemäß DIN 53 453 bei 23°C jeweils an 10 Prüfkörpern. Die Messung der Wärmeformbeständigkeit erfolgte durch Bestimmung der Vicat-B-Erweichungstemperatur gemäß DIN 53 460. Die Fließfähigkeit der Polymeren in der Schmelze wird durch Messung des Schmelzindex (MFI) bei 320°C und 21,6 kg Belastung gemäß DIN 53 735 beurteilt.The Charpy impact strength a k was tested on standard small bars according to DIN 53 453 at 23 ° C on 10 test specimens each. The heat resistance was measured by determining the Vicat B softening temperature in accordance with DIN 53 460. The flowability of the polymers in the melt is assessed by measuring the melt index (MFI) at 320 ° C. and a load of 21.6 kg in accordance with DIN 53 735.

Beispiele 1-4Examples 1-4

Aus 10 gew.-%igen Lösungen von Polyester "APE" und Polycarbonat "PC" wurde auf einem Doppelwellen-Ausdampfextruder aromatisches Polyestercarbonat hergestellt. Die Temperatur im letzten Vakuumextrusionsteil betrug 320°C.Aromatic polyester carbonate was produced from 10% by weight solutions of polyester "APE" and polycarbonate "PC" on a twin-screw evaporation extruder. The temperature in the last vacuum extrusion was 320 ° C.

Vergleichsbeispiele 1-2Comparative Examples 1-2

Polyester "APE" und Polycarbonat "PC" wurden in Form ihrer Granulate gemischt und bei 360°C auf einem Vakuum-Doppelwellenextruder extrudiert.

Figure imgb0003
Polyester "APE" and polycarbonate "PC" were mixed in the form of their granules and extruded at 360 ° C on a vacuum twin-screw extruder.
Figure imgb0003

Claims (6)

1. Verfahren zur Herstellung aromatischer Polyestercarbonate mit einem molaren Verhältnis von Ester zu Carbonatgruppen von 20:1 bis 1:20, dadurch gekennzeichnet, daß man eine lösungsmittelhaltige Mischung, die a) aromatischen Polyester und b) aromatisches Polycarbonat im gewünschten Verhältnis und 5 bis 80 Gew.-% organisches Lösungsmittel (bezogen auf lösungsmittelhaltige Mischung) enthält, unter Abzug des Lösungsmittels - gegebenenfalls unter vermindertem Druck - und unter Einwirkung von Scherkräften - vorzugsweise beginnend in einem Temperaturbereich von 150 bis 280°C - unter Aufrechterhalten des flüssigen Zustands auf eine Temperatur von 300 bis 420°C, erhitzt, bis das Reaktionsprodukt nur noch eine Glasübergangstemperatur aufweist.1. A process for the preparation of aromatic polyester carbonates with a molar ratio of ester to carbonate groups of 20: 1 to 1:20, characterized in that a solvent-containing mixture, the a) aromatic polyester and b) aromatic polycarbonate in the desired ratio and 5 to 80 Wt .-% organic solvent (based on solvent-containing mixture) contains, with the deduction of the solvent - optionally under reduced pressure - and under the action of shear forces - preferably starting in a temperature range of 150 to 280 ° C - while maintaining the liquid state at a temperature from 300 to 420 ° C, heated until the reaction product has only a glass transition temperature. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die lösungsmittelhaltige Mischung 20-70 Gew.-% organisches Lösungsmittel enthält.2. The method according to claim 1, characterized in that the solvent-containing mixture contains 20-70 wt .-% organic solvent. 3. Verfahren nach Ansprüchen 1 und 2, dadurch gekennzeichnet, daß man das Verfahren in einem Temperaturbereich von 200 bis 260°C beginnt.3. Process according to Claims 1 and 2, characterized in that the process is started in a temperature range from 200 to 260 ° C. 4. Verfahren nach Ansprüchen 1-3, dadurch gekennzeichnet, daß man die Reaktionsmischung auf 310 bis 360°C erhitzt.4. Process according to claims 1-3, characterized in that the reaction mixture is heated to 310 to 360 ° C. 5. Verfahren nach Anspruch 1-4, dadurch gekennzeichnet, daß das Lösungsmittel aus der Reihe Methylenchlorid, Chloroform, Tetrachlorethane, Trichlorethylen, Tetrachlorethylen, Chlorbenzol, Dichlorbenzol, Toluol, Xylol, Anisol und deren Mischungen ausgewählt ist.5. The method according to claim 1-4, characterized in that the solvent is selected from the series of methylene chloride, chloroform, tetrachloroethane, trichlorethylene, tetrachlorethylene, chlorobenzene, dichlorobenzene, toluene, xylene, anisole and mixtures thereof. 6. Nach Verfahren gemäß Ansprüchen 1-5 hergestellte Polyestercarbonate.6. Polyester carbonates produced by the process according to claims 1-5.
EP83105763A 1982-06-26 1983-06-13 Aromatic polyester carbonate with impact strenght, and process for its preparation Expired EP0097861B1 (en)

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DE3223980 1982-06-26
DE19823223980 DE3223980A1 (en) 1982-06-26 1982-06-26 AROMATIC POLYESTER CARBONATES WITH HIGH IMPACT STRENGTH AND METHOD FOR THE PRODUCTION THEREOF

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EP0097861B1 EP0097861B1 (en) 1986-03-05

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JP (1) JPS598725A (en)
CA (1) CA1241486A (en)
DE (2) DE3223980A1 (en)

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EP0347169A2 (en) * 1988-06-16 1989-12-20 Mitsui Petrochemical Industries, Ltd. Polyester carbonate copolymers processes for preparing same and polyester resin compositions containing said copolymers
EP0372919A2 (en) * 1988-12-07 1990-06-13 E.I. Du Pont De Nemours And Company End-capping of polyarylate carboxyl acid ends by use of aromatic carbonates

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JP3122721B2 (en) * 1989-12-28 2001-01-09 日本ジーイープラスチックス株式会社 Polycarbonate composition and method for producing the same
US5196488A (en) * 1991-08-22 1993-03-23 Eastman Kodak Company Blend of a polyester and a polycarbonate
US5252680A (en) * 1991-08-22 1993-10-12 Eastman Kodak Company Blend of a polyester and a polycarbonate
US5194522A (en) * 1991-08-22 1993-03-16 Eastman Kodak Company Blend of a polyester and a polycarbonate
US5202393A (en) * 1991-08-22 1993-04-13 Eastman Kodak Company Blend of a polyester and a polycarbonate
US5194520A (en) * 1991-08-22 1993-03-16 Eastman Kodak Company Blend of a polyester and a polycarbonate
US5194521A (en) * 1991-08-22 1993-03-16 Eastman Kodak Company Blend of a polyester and a polycarbonate
US5202392A (en) * 1991-08-22 1993-04-13 Eastman Kodak Company Blend of a polyester and a polycarbonate
WO2008053528A1 (en) 2006-10-31 2008-05-08 Daishowa Seiki Co., Ltd. Tap holder
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EP0347169A2 (en) * 1988-06-16 1989-12-20 Mitsui Petrochemical Industries, Ltd. Polyester carbonate copolymers processes for preparing same and polyester resin compositions containing said copolymers
EP0347169A3 (en) * 1988-06-16 1991-03-13 Mitsui Petrochemical Industries, Ltd. Polyester carbonate copolymers processes for preparing same and polyester resin compositions containing said copolymers
EP0372919A2 (en) * 1988-12-07 1990-06-13 E.I. Du Pont De Nemours And Company End-capping of polyarylate carboxyl acid ends by use of aromatic carbonates
EP0372919A3 (en) * 1988-12-07 1991-07-24 E.I. Du Pont De Nemours And Company End-capping of polyarylate carboxyl acid ends by use of aromatic carbonates

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DE3223980A1 (en) 1983-12-29
DE3362413D1 (en) 1986-04-10
US4533702A (en) 1985-08-06
EP0097861B1 (en) 1986-03-05
CA1241486A (en) 1988-08-30
JPS598725A (en) 1984-01-18

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